Electrochromic device including a transparent conductive oxide layer and a bus bar and a process of forming the same

ABSTRACT

An electrochromic device can include a substrate, a transparent conductive oxide layer over the substrate, and a bus bar over the substrate. The bus bar can include silver and has a resistivity of at most 6.7×10 −6  Ω*cm, an average adhesion strength to SiO 2  of at least 3N based on 20 measurements, as determined by Method A of ASTM B905-00 (Reapproved 2010), or a classification of at least 4, as determined by Method B of ASTM B905-00 (Reapproved 2010). In another aspect a process of forming an electrochromic device can include forming a transparent conductive oxide layer over a substrate; forming a bus bar precursor over the substrate, wherein the precursor includes silver; and firing the precursor to form a bus bar. Firing can be performed such that the first bus bar is at a temperature of at least 390° C.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of and claims priority under 35U.S.C. 120 to U.S. patent application Ser. No. 15/487,133, filed Apr.13, 2017, entitled “Electrochromic Device Including a TransparentConductive Oxide Layer and a Bus Bar and a Process of Forming the Same,”naming as an inventor Sophie Brossard, which claims priority under 35U.S.C. 119(e) to U.S. Provisional Patent Application No. 62/324,496,filed Apr. 19, 2016, entitled “Electrochromic Device Including a Bus BarHaving Low Resistivity and Good Adhesion and a Process of Forming theSame,” naming as an inventor Sophie Brossard, of which both applicationsare assigned to the current assignee hereof and incorporated herein byreference in their entireties.

FIELD OF THE DISCLOSURE

The present disclosure is directed to electrochromic devices, and morespecifically to electrochromic devices including transparent conductivelayers and bus bars and processes of forming the same.

BACKGROUND

An electrochromic device helps to a room of a building or passengercompartment of a vehicle from becoming too warm. The electrochromicdevice includes bus bars that can be biased and allow the electrochromicdevice to change from a higher transmission state to a lowertransmission state to reduce the transmission of near infraredradiation. The bus bars are desired to have low resistivity and goodadhesion to underlying materials. One or more layers in theelectrochromic device may limit the selection of materials andprocessing conditions for the bus bars. Accordingly, improvement in theresistivity and adhesion of the bus bars is desired.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments are illustrated by way of example and are not limited in theaccompanying figures.

FIG. 1 includes a flow diagram for a process of forming anelectrochromic device in accordance with an embodiment as describedherein.

FIG. 2 includes an illustration of a cross-sectional view of a workpieceincluding a substrate and an electrochromic stack.

FIG. 3 includes an illustration of a cross-sectional view of theworkpiece of FIG. 2 after forming an oxidation-resistant layer.

FIG. 4 includes an illustration of a cross-sectional view of theworkpiece of FIG. 3 after forming a layer having a refractive indexbetween the refractive indices of the oxidation-resistant layer and anambient.

FIG. 5 includes an illustration of a cross-sectional view of theworkpiece of FIG. 4 after patterning the electrochromic stack.

FIG. 6 includes an illustration of a cross-sectional view of theworkpiece of FIG. 5 after forming bus bars.

FIG. 7 includes an illustration of a cross-sectional view of theworkpiece of FIG. 6 after forming a substantially completedelectrochromic device.

FIG. 8 includes illustration of a cross-sectional view of an insulatedglass unit that includes the electrochromic device of FIG. 7.

Skilled artisans appreciate that elements in the figures are illustratedfor simplicity and clarity and have not necessarily been drawn to scale.For example, the dimensions of some of the elements in the figures maybe exaggerated relative to other elements to help to improveunderstanding of embodiments of the invention.

DETAILED DESCRIPTION

The following description in combination with the figures is provided toassist in understanding the teachings disclosed herein. The followingdiscussion will focus on specific implementations and embodiments of theteachings. This focus is provided to assist in describing the teachingsand should not be interpreted as a limitation on the scope orapplicability of the teachings.

Polymers include homopolymers and co-polymers. A homopolymer is formedfrom a single polymeric precursor, and a co-polymer is formed fromdifferent polymeric precursors.

In this specification, refractive indices are measured at 550 nm.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having,” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of features is notnecessarily limited only to those features but may include otherfeatures not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive-or and not to an exclusive-or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

The use of “a” or “an” is employed to describe elements and componentsdescribed herein. This is done merely for convenience and to give ageneral sense of the scope of the invention. This description should beread to include one or at least one and the singular also includes theplural, or vice versa, unless it is clear that it is meant otherwise.

The use of the word “about”, “approximately”, or “substantially” isintended to mean that a value of a parameter is close to a stated valueor position. However, minor differences may prevent the values orpositions from being exactly as stated. Thus, differences of up to tenpercent (10%) for the value are reasonable differences from the idealgoal of exactly as described.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. The materials, methods, andexamples are illustrative only and not intended to be limiting. To theextent not described herein, many details regarding specific materialsand processing acts are conventional and may be found in textbooks andother sources within the glass, vapor deposition, and electrochromicarts.

An electrochromic device can include a bus bar that has low resistivityand good adhesion to underlying materials, such as a transparentconductive oxide and a substrate, each of which may be in physicalcontact with the bus bar. The electrochromic device can include asubstrate, a transparent conductive oxide layer over the substrate, anda bus bar over the substrate. The bus bar can include silver and have aresistivity of at most 8.0×10⁻⁶ Ω*cm; an average adhesion strength toSiO₂ of at least 3 N based on 20 measurements, as determined by Method Aof ASTM B905-00 (Reapproved 2010); a classification of at least 3, asdetermined by Method B of ASTM B905-00 (Reapproved 2010); or anycombination thereof.

In another aspect, a process of forming an electrochromic device caninclude forming a transparent conductive oxide layer over a substrate;forming a bus bar precursor over the substrate, wherein the bus barprecursor includes silver; and firing the bus bar precursor to form abus bar, wherein firing is performed such that the bus bar is at atemperature of at least 390° C.

An oxidation-resistant layer can be used to reduce the likelihood that atransparent conductive oxide is significantly adversely affected duringthe formation of the bus bars. The oxidation-resistant layer can allowfor silver-based frits to be used that have relatively higher sinteringtemperatures as compared an electrochromic device formed with theoxidation-resistant layer. In a particular embodiment, theoxidation-resistant layer helps the transparent conductive oxide frombecoming too oxidized, which is undesired as the transparent conductiveoxide needs to have an acceptable resistivity.

An oxidation-resistant layer may also be used between the substrate andan electrochromic stack. Such an embodiment may be helpful in reducingthat mobile ions, such as Li⁺, Na⁺, or the like, may migrate from thesubstrate (e.g., soda lime glass) to the electrochromic stack or fromthe electrochromic stack to the substrate. In another embodiment,oxidation-resistant layers may lie along opposite major surfaces of theelectrochromic stack.

When the oxidation-resistant layer is adjacent to air or another gas, acapping layer can be disposed between the oxidation-resistant layer andair or other gas. The capping layer can have a refractive index that isbetween the refractive indices of the oxidation-resistant layer and airor the other gas. The capping layer can help in reducing totalreflection.

The embodiments as illustrated in the figures and described below helpin understanding particular applications for implementing the conceptsas described herein. The embodiments are exemplary and not intended tolimit the scope of the appended claims.

FIG. 1 includes a process flow of forming an electrochromic device inaccordance with an embodiment. The process can include forming anelectrochromic stack over a substrate, at block 102. FIG. 2 includes anillustration of a cross-section view of a partially fabricatedelectrochromic device after forming an electrochromic stack. Theelectrochromic device can include a transparent substrate 200 thatincludes a glass substrate, a sapphire substrate, an aluminum oxynitride(AlON) substrate, a spinel substrate, or a transparent polymer. In aparticular embodiment, the transparent substrate 200 can includeultra-thin glass that is a mineral glass having a thickness in a rangeof 50 microns to 300 microns. The transparent polymer can include apolyacrylate, a polyester, a polycarbonate, a polysiloxane, a polyether,a polyvinyl compound, another suitable class of transparent polymer, ora mixture thereof. In another embodiment, the transparent substrate 200can be a laminate including layers of the materials that make up thepreviously described transparent substrates. In another embodiment, thelaminate can include a solar control layer that reflects ultravioletradiation or a low emissivity material. The substrate 200 may or may notbe flexible.

In an embodiment, the transparent substrate 200 can be a glass substratethat can be a mineral glass including SiO₂ and one or more other oxides.Such other oxides can include Al₂O₃, an oxide of an alkali metal, anoxide of an alkaline earth metal, B₂O₃, ZrO₂, P₂O₅, ZnO, SnO₂, SO₃,As₂O₂, or Sb₂O₃. The transparent substrate 200 may include a colorant,such as oxides of iron, vanadium, titanium, chromium, manganese, cobalt,nickel, copper, cerium, neodymium, praseodymium, or erbium, or a metalcolloid, such as copper, silver, or gold, or those in an elementary orionic form, such as selenium or sulfur.

In an embodiment in which the transparent substrate 200 is a glasssubstrate, the glass substrate is at least 50 wt % SiO₂. In anembodiment, the SiO₂ content is in a range of 50 wt % to 85 wt %. Al₂O₃may help with scratch resistance, for example, when the major surface isalong an exposed surface of the laminate being formed. When present,Al₂O₃ content can be in a range of 1 wt % to 20 wt %. B₂O₃ can beusefully used to reduce both the viscosity of the glass and its thermalexpansion coefficient. The B₂O₃ content may be no greater than 20 wt %,and in a particular embodiment, less than 15 wt %. Alkaline earth metalsinclude magnesium, calcium, strontium, and barium. The oxides of analkaline earth metal are useful for reducing the viscosity of the glassand facilitating fusion, without heavily penalizing the expansioncoefficient. Calcium and magnesium have a relatively low impact on thedensity of the glass as compared to some of the other oxides. The totalcontent of alkaline metal oxide may be no greater than 25 wt %, 20 wt %,or 15 wt %. Oxides of an alkali metal can reduce viscosity of the glasssubstrate and its propensity to devitrify. The total content of alkalimetal oxides may be at most than 8 wt. %, 5 wt. %, or 1 wt. %. In someapplications, the glass substrate is desired to be clear, and thus, thecontent of colorants is low. In a particular embodiment, the ironcontent is less than 200 ppm.

The glass substrate can include heat-strengthened glass, tempered glass,partially heat-strengthened or tempered glass, or annealed glass.“Heat-strengthened glass” and “tempered glass”, as those terms are knownin the art, are both types of glass that have been heat treated toinduce surface compression and to otherwise strengthen the glass.Heat-treated glasses are classified as either fully tempered orheat-strengthened. In an embodiment, the glass substrate is temperedglass and has a surface compression of about 69 MPa or more and an edgecompression of about 67 MPa or more. In another embodiment, thetransparent substrate is heat-strengthened and has a surface compressionin a range of 24 MPa to 69 MPa and an edge compression between 38 MPaand 67 MPa. The term “annealed glass” means glass produced withoutinternal strain imparted by heat treatment and subsequent rapid cooling.Thus annealed glass only excludes heat-strengthened glass or temperedglass. The glass substrate can be laser cut.

A transparent conductive oxide layer 202 overlies the transparentsubstrate 200. The transparent conductive oxide layer 202 can includedoped metal oxide. The doped metal oxide can include a zinc oxide or atin oxide, either of which may be doped with a Group 13 element, such asAl, Ga, or In. Indium tin oxide (ITO) and aluminum zinc oxide (AZO) areexemplary, non-limiting materials that can be used. As illustrated inFIG. 2, the transparent conductive oxide layer 202 has a cut to allow asubsequently-formed bus bar to contact the right-hand portion of thetransparent conductive oxide layer 202 without electrically shortingsuch bus bar to the left-hand portion of the transparent conductiveoxide layer 202. The transparent conductive oxide layer 202 has athickness in a range of 150 nm to 600 nm.

An electrode layer 204, an electrolyte layer 206, and another electrodelayer 208 overlie the transparent conductive oxide layer 202 and thetransparent substrate 200. The electrode layer 204 can be one of theelectrochromic (EC) layer or the counter electrode (CE) layer, and theelectrode layer 208 is the other of the CE layer or the EC layer.

The EC layer can have a variable transmission of visible light and nearinfrared radiation (e.g., electromagnetic radiation having wavelengthsin a range of 700 nm to 2500 nm) depending on the biasing conditions.For example, in the absence of an electrical field, the electrochromicdevice is in a high transmission (“bleached”) state, and an electricalfield can cause mobile ions, such as Li⁺, Na⁺, or H⁺, to migrate fromthe CE layer, through the electrolyte layer to the EC layer and reducethe transmission of visible light and near infrared radiation throughthe electrochromic device. The lower transmission state may also bereferred to as a tinted or colored state. The EC layer can include anoxide of a transition metal, such as iridium, rhodium, ruthenium,tungsten, manganese, cobalt, or the like. In a particular embodiment,the CE layer includes WO₃. As initially formed, the EC layer may notinclude any significant amount of the mobile ions that cause the EClayer to have a reduced transmission. In another embodiment, the EClayer may include at least some mobile ions, however, the electrochromicdevice may be reverse biased to move the mobile ions from the EC layer,through the electrolyte layer 206 to the CE layer. In an embodiment, thethickness of the EC layer as deposited is in a range 80 nm to 600 nm.

The CE layer can provide a principal source of mobile ions. Furthermore,the CE layer remains substantially transparent to visible light when theelectrochromic device is in its high transmission state or its lowtransmission state. The CE layer can include an oxide of transitionmetal element. In embodiment, the CE layer can include an oxide ofnickel. The nickel may be in its divalent state (Ni²⁺), its trivalentstate (Ni³⁺), or a combination thereof. The CE layer can include anoxide of a transition metal element, such as such as iridium, rhodium,ruthenium, tungsten, manganese, cobalt, or the like. The CE layer canalso provide the source of mobile ions that can pass through theelectrolyte layer 206. The source of mobile ions may be incorporatedinto the CE layer as it is formed. In a finished device, the CE layermay be represented by a chemical formula of:A_(x)Ni²⁺ _((1-y))Ni³⁺ _(y)M_(z)O_(a),

where:

A is an element that produces a mobile ion, such as Li, Na, or H;

M is a metal; and0<x≤10,0≤y≤1,0≤z≤10, and (0.5x+1+0.5y+z)≤a≤(0.5x+1+0.5y+3.5z).

In a particular non-limiting embodiment, A is Li, M is W, and, in afinished device, the CE layer may be represented by a chemical formulaof:Li_(x)Ni²⁺ _((1-y))Ni³⁺ _(y)W_(z)O_((1+0.5x+0.5y+3z)),

where 1.5≤x≤3, 0.4≤y≤0.95, and 0.15≤z≤1.

In an embodiment, the thickness of the CE layer is in a range 80 nm to500 nm.

The electrolyte layer 206 includes a solid electrolyte that allows ionsto migrate through the electrolyte layer 206 as the electrical fieldacross the electrolyte layer is changed from the high transmission stateto the low transmission state, or vice verse. In an embodiment, theelectrolyte layer 206 can be a ceramic electrolyte. In anotherembodiment, the electrolyte layer 206 can include a silicate-based orborate-based material. The electrolyte layer 206 may include a silicate,an aluminum silicate, an aluminum borate, a borate, a zirconiumsilicate, a niobate, a borosilicate, a phosphosilicate, a nitride, analuminum fluoride, or another suitable ceramic material. Other suitableion-conducting materials can be used, such as tantalum pentoxide or agarnet or perovskite material based on a lanthanide-transition metaloxide. In another other embodiment, as formed, the electrolyte layer 206may include mobile ions. Thus, lithium-doped or lithium-containingcompounds of any of the foregoing may be used. The electrolyte layer 206may include a plurality of layers having alternating or differingmaterials, including reaction products between at least one pair ofneighboring layers. In a further embodiment, the refractive index andthickness of the electrolyte layer 206 are selected to have acceptablevisible light transmission while keeping electronic current very low. Inanother embodiment, the electrolyte layer 206 has low or no significantelectronic conductivity (e.g., low leakage current). The thickness ofthe electrolyte layer 206 can be in a range of 10 nm to 70 nm.

A transparent conductive oxide layer 210 overlies the transparentsubstrate 200, the transparent conductive oxide layer 202, the electrodelayer 204, the electrolyte layer 206, and the electrode layer 208. Thetransparent conductive oxide layer 210 can include any of the materialsas previously described with respect to the transparent conductive oxidelayer 202. The transparent conductive oxide layer 210 can include thesame material or a different material, as compared to the transparentconductive oxide layer 202. The transparent conductive oxide layer 210has a thickness in a range of 150 nm to 600 nm.

The layers within the electrochromic stack can be formed by physicalvapor deposition, chemical vapor deposition, atomic layer deposition,another suitable technique, or any combination thereof.

The method can further include forming an oxidation-resistant layer overthe electrochromic stack, at block 122 in FIG. 1. Theoxidation-resistant layer helps to protect underlying layers during athermal cycle used in annealing or curing subsequently-formed bus bars,heating to bend the substrate 200 to a desired curvature or shape, oranother purpose. The performance of one or more of the layers within theelectrochromic stack may be adversely affected by the thermal cycle. Ina particular embodiment, the transparent conductive oxide layer 202 and210 may include a transparent conductive oxide that is partially, andnot fully, oxidized. If the transparent conductive oxide would becomefully oxidized, the transparent conductive oxide may not have sufficientconductivity and may become too resistive or an insulator if fullyoxidized. The oxidation-resistant layer helps to protect the transparentconductive oxide layer 202, 210, or both from becoming too oxidized.

FIG. 3 includes an illustration of the electrochromic device afterforming an oxidation-resistant layer 302 over the transparent conductiveoxide layer 210. The oxidation-resistant layer 302 can include anitride, such as silicon nitride, aluminum nitride, titanium nitride,tungsten nitride, tantalum nitride, titanium silicon nitride, tungstensilicon nitride, tantalum silicon nitride, or another metal nitride. Ina particular embodiment, the oxidation-resistant layer 302 includessilicon nitride. The thickness of the oxidation-resistant layer 302 isselected to provide sufficient transmission of visible light. In anembodiment, the thickness of the oxidation-resistant layer is in a rangeof at least 10 nm to 20 nm in order to provide a continuous layer, andin another embodiment the thickness is at most 300 nm or at most 250 nm,as a greater thickness may cause too much compressive stress that couldresult in delamination. In a particular embodiment, the compressivestress may be at most 1 GPa. In a particular embodiment, the thicknessis in a range of 50 nm to 100 nm to allow a continuous layer withsufficient oxidation resistance to be formed without causing too muchstress.

The method can further include forming a layer having an intermediateindex of refraction over the oxidation-resistant layer, at block 12 inFIG. 1. The oxidation-resistant layer 302 can have a relatively highindex of refraction, and if a major surface of the oxidation-resistantlayer 302 would be exposed to air or another gas, the relativedifference in the indices of refraction could cause the total reflectionto be too high. Thus, the layer having the intermediate index ofrefraction that is between the indices of refraction of theoxidation-resistant layer and air or another gas can help to reducetotal reflection.

FIG. 4 includes an illustration of the electrochromic device afterforming a capping layer 402 having an intermediate index of refractionover the oxidation-resistant layer 302. The capping layer 402 can be aninsulating layer. In an embodiment, the capping layer 402 can include anoxide, such as a silicon oxide or another suitable oxide. The oxide mayor may not be porous. For example, a mixture of the oxide and organicparticles can be applied, and the organic particles may be burned offduring a subsequent firing, leaving a porous oxide.

The thickness of the layer 402 can be sufficiently thick to affectsignificantly the total reflection. In practice, sputtering SiO₂ is arelatively slow process, thus, an upper value may be limited byequipment throughput. In terms of actual thickness, in a particularembodiment, the capping layer 402 can have a thickness of at least 30nm, at least 40 nm, or at least 50 nm, and in another particularembodiment, the capping layer 402 can have a thickness of at most 200nm, at most 150 nm, or at most 150 nm. In terms of ranges, the cappinglayer 402 may have a thickness in a range of 30 nm to 200 nm, 40 to 150nm, or 50 nm to 120 nm.

The layers 302 and 402 can be formed by physical vapor deposition,chemical vapor deposition, atomic layer deposition, another suitabletechnique, or any combination thereof.

The method can include removing portions of the electrochromic stack atareas where bus bars will be subsequently formed, at block 142 ofFIG. 1. Referring to FIG. 4, one of the bus bars will be electricallyconnected to the transparent conductive oxide layer 202 near theleft-hand side of FIG. 4, and another bus bar will be electricallyconnected to the transparent conductive oxide layer 202 near theright-hand side of FIG. 4. The removal of the portions of theelectrochromic stack may be performed using an ablating technique, suchas laser ablation, or may be removed using an etching technique. Asillustrated in FIG. 5, the layers 204, 206, 208, 210, 302, and 402 arepatterned to define openings 502 and 504, in which the transparentconductive oxide layer 202 is exposed. In another embodiment, theopening 504 may extend to a different depth as compared to opening 502.For example, the opening 504 may extend to a variety of differentdepths, so long that the transparent conductive oxide layer 210 isexposed within the opening 504. In an embodiment, the layers 302 and 402are patterned, and the transparent conductive layer 210 is exposed alongthe bottom of the opening 504. In another embodiment, the opening 504can be extended through the transparent conductive oxide layer 202 suchthat the substrate 200 is exposed along the bottom of the opening 504.After reading this specification, skilled artisans will be able todetermine a depth for the opening 504 that meets the needs or desiresfor a particular application.

The method can further include depositing a bus bar precursor, at block144 in FIG. 1, and firing the bus bar precursor to form bus bars, atblock 146. The bus bar precursor can include silver, and thus, the busbars can include silver. In an embodiment, the bus bar precursor can bea silver paste. The use of the oxidation-resistant layer 302 allows agreater selection of silver-containing frits to be used and moreaggressive firing conditions. For example, silver-containing frits thatneed a higher firing temperature, a more reactive ambient during firing,or any combination thereof may be used. Before the invention as claimedherein, the selection of silver-containing frits and firing conditionswere limited, as the transparent conductive oxide layer 210 would beadversely affected by firing conditions that could cause the transparentconductive oxide layer 210 to become too oxidized. For example, asilver-containing frit may be fired at a temperature at lower than 390°C. in order to not significantly adversely affecting the transparentconductive oxide layer 210. However, firing at such a relatively lowtemperature provides relative high resistivity and poorer adhesion ofthe bus bars to the underlying materials that contact the bus bars, suchas the transparent conductive oxide layer 202 and the substrate 200(e.g., a mineral glass material).

The oxidation-resistant layer 302 can help to reduce the likelihood thatthe transparent conductive oxide layer 210 will be significantlyadversely affected by more aggressive firing conditions. Accordingly, awider variety of silver-containing frits and firing conditions may beused. Firing temperatures of at least 390° C. can be used and providebus bars having lower resistivity and better adhesion to underlyingmaterials.

FIG. 6 includes as illustration after forming the bus bars 602 and 610.Some of the deposition and firing parameters can depend on the desiredproperties of the bus bars 602 and 610 after firing has been performed.The bus bars 602 and 610 can have a resistivity of at most 8.0×10⁻⁶Ω*cm. In another embodiment, the resistivity is at most 6.0×10⁻⁶ Ω*cm,at most 5.0×10⁻⁶ Ω*cm, at most 4.0×10⁻⁶ Ω*cm, or at most 3.0×10⁻⁶ Ω*cm.Firing temperatures can provide for a lower resistivity. The resistivitywill be higher than the resistivity of pure silver as reported inchemistry handbooks, and therefore, the resistivity is greater than1.59×10⁻⁸ Ω*cm. The thickness of the bus bars 602 and 610, incombination with the resistivity, affect the sheet resistivity. In anembodiment, the thickness of the bus bars 602 and 610 can be at least 2microns, at least 7 microns, or at least 12 microns. Although atheoretical upper limit in not known, the maximum thickness may dependon the application. In another embodiment, the thickness can be at most80 microns, at most 60 microns, or at most 40 microns. For manyapplications, the thickness of the bus bars 602 and 610 are in a rangeof 12 microns to 40 microns. After reading this specification, skilledartisans will be able to determine a thickness to provide needed ordesired electrical properties of the bus bars 602 and 610.

The bus bar precursor can be deposited by printing, silk screening, orthe like. The bus bar precursor can have a thickness sufficient toachieve the desired thickness of the bus bars 602 and 610 after the busbar precursor is fired. The bus bar precursor thickness can depend onthe amount of solvent, resin, or other organic or volatile componentswithin the precursor. The bus bar precursor may be deposited to athickness that is 1.1 times to 4 times the thickness of the bus bars 602and 610 after firing. As a non-limiting example, if the bus bars 602 to610 are to have a thickness after firing of 20 microns, the bus barprecursor can be deposited to a thickness in a range of 22 microns to 80microns.

The bus bar precursor can be fired to form the bus bars 602 and 610. Thefiring may performed at one or more temperatures. In an embodiment, thesubstrate 200 can be heated to a temperature in a range of approximately100° C. to 350° C. to evaporate solvent, burn off resin, volatilize anyother organic material, or any combination thereof, if any solvent,resin, or other organic material is within the bus bar precursor. Thetemperature of the substrate 200 is increased to a sintering temperatureto sinter the silver-based frit in the bus bar precursor. Thetemperature of the substrate 200 can be at least 390° C., at least 400°C., at least 425° C., at least 450° C., or at least 475° C. Theresistivity of the bus bars 602 and 610 can be lowered and adhesion tounderlying materials can be increased, as higher temperatures can now beused for sintering. The presence of the oxidation-resistant layer 302during firing helps to reduce the likelihood that the transparentconductive oxide layer 210 will be significantly adversely affectedduring firing. Thus, a variety of ambients may be used during firing. Inan embodiment, the firing can be performed in an inert gas (N₂, Ar, orthe like) or can include a combination of inert and oxidizing gases (O₂,N₂O, or the like). In a particular embodiment, the ambient includes air.In another embodiment, the firing may be performed in an oxidizing gaswithout an inert gas. The time during the sintering portion can be in arange of 2 minutes to 120 minutes. The particular time may depend on thecomposition of the silver-based frit, and thus, a commercial providermay provide a recommended time range for the sintering portion offiring.

In an embodiment, the firing as previously described may be performed asa separate operation or may occur during a heat cycle performed foranother purpose. Thus, the timing of when the firing is performed isflexible, allowing users more latitude in integrating the firing into anexisting process flow. Furthermore, the different parts of the firingoperation may be performed at different points in a process flow. Forexample, solvents can be evaporated from the bus bar precursors, resincan be burned off, any other organic material can be volatilized, or anycombination thereof can be performed during one heat cycle; andsintering can be performed during a different heat cycle. One or moreother process operations may be performed between the different heatcycles, if needed or desired.

The method can further include performing finishing operations, at block162 in FIG. 1. The particular finishing operation may depend on theparticular application. As illustrated in FIG. 7, portions of the layers210, 302, and 402 are removed at opening 702, so that the bus bar 602 isnot electrically connected to most of the transparent conductive oxidelayer 210. Thus, the bus bar 602 is a principal connection for thetransparent conductive oxide layer 202, and the bus bar 610 is aprincipal connection for the transparent conductive oxide layer 210. Atthis point in the process, an electrochromic device 700 is formed. Inanother embodiment (not illustrated), the bus bar 602 is formed suchthat it does not contact the side of the stack within the opening 502,as illustrated in FIG. 5. In this embodiment, the removal of theportions of the layers 210, 302, and 402 is not needed.

In a further embodiment, the electrochromic device 700 can be at least apart of a window for a vehicle. In a vehicle application, theelectrochromic device 700 may be bent or otherwise shaped to conform tothe body shape of the vehicle. The temperature for bending or otherwiseshaping the electrochromic device can be in a temperature of at least600° C. In a particular embodiment, the temperature is in a range of600° C. to 700° C. The heat may be applied locally. Theoxidation-resistant layer 302 can help to reduce the likelihood ofsignificantly adversely affecting the transparent conductive oxide layer210 during bending or otherwise shaping. The sintering portion of firingto form the bus bars may occur during the heat cycle used to bend theelectrochromic device.

In an embodiment, an insulated glass unit 800 may be formed, asillustrated in FIG. 8. The electrochromic device 700 can be coupled to acounter substrate 802 that is transparent to visible light. The countersubstrate 802 may include a tempered or strengthened glass. In aparticular embodiment, an adhesive (not illustrated) can be used betweenthe electrochromic device 700 and the counter substrate 802. Theinsulated glass unit 800 can further include a glass panel 804, spacers822, and a sealing material 824. Similar to the counter substrate 802,the glass panel 804 can include a tempered or strengthened glass.Furthermore, the glass panel 804 may be part of a laminate that caninclude a solar control layer, similar to the solar control layer aspreviously described with respect to the substrate 200. The insulatedglass unit may include a solar control layer within the substrate 200and not the glass panel 804, a solar control layer within or attached tothe glass panel 804, or solar control layer with each of the substrate200 and within or attached to the glass panel 804 may be used. In thislast alternative, the solar control layers may serve differentfunctions. For example, the solar control layer closer to the outside ofa building may help to reject near infrared radiation, and the othersolar control layer closer to the inside of the building may include alow emissivity material or help to reject ultraviolet radiation. Duringa sealing operation, an inert gas, such as argon, N₂, or the like, mayfill the gap 806.

Optionally, after forming the electrochromic device 700, theelectrochromic device 700 may be annealed to reduce stress or foranother purpose. The anneal may be performed separately from the firing.In another embodiment, the sintering portion of the firing may becombined with the anneal operation. The oxidation-resistant layer 302can allow a higher temperature for the anneal, an oxidizing ambient,such as air, or both to be used without significantly adverselyaffecting the transparent conductive oxide layer 210. The anneal may beperformed at a temperature in a range of 100° C. to 600° C.

Embodiments can provide benefits as compared to conventionalelectrochromic devices. The higher temperature during the sinteringportion of the firing of the bus bars allows for a wider array ofsilver-based frits to be used. Before the invention, the temperatureduring firing would be limited so that the transparent conductive oxidelayer 210 would not oxidize too much. As the firing temperatureincreases, the likelihood of significantly affecting the transparentconductive oxide increases. When an oxidizing ambient is used duringfiring, the transparent conductive oxide may become too oxidized, andthe bus bars will be too resistive. Silver-based frits that do notsufficiently sinter at temperatures of lower than 390° C. can now beused. Such silver-based frits can provide lower resistivity thansilver-based frits designed to be sintered at temperatures of less than390° C., even when the same sintering temperature is used.

The ability to use a higher temperature during the sintering can allowfor better adhesion of the bus bars to underlying materials. The busbars may contact a layer within an electrochromic stack and thesubstrate. In the embodiment as illustrated, the bus bars 602 and 610contact the transparent conductive oxide layer 202 and the substrate 200at an area away from the electrochromic stack. In a particularembodiment, the transparent conductive oxide layer 202 can be atransparent conductive oxide, and the surface of the substrate 200contacting the bus bars 602 and 610 can be a mineral glass that includesSiO₂. ASTM B905-00 (Reapproved) 2010 can be used to test for adhesion toSiO₂. In an embodiment using Method A of the ASTM standard, the averageadhesion strength to SiO₂ is at least 3 N, at least 5 N, or at least 7 Nbased on 20 measurements. Although there is no theoretical limit ofadhesion that would be problematic, the average adhesion strength(Method A) may be less than 1000 N. Very good adhesion strength may beconsidered at least 15 N. Although there is no theoretical limit ofadhesion that would be problematic, the average adhesion strength(Method A) may be less than 1000 N. Very good adhesion strength may beconsidered at least 15 N. In an embodiment using Method B of the ASTMstandard, the average adhesion strength to SiO₂ is at least 3 or atleast 4 based on 20 measurements.

Many different aspects and embodiments are possible. Some of thoseaspects and embodiments are described below. After reading thisspecification, skilled artisans will appreciate that those aspects andembodiments are only illustrative and do not limit the scope of thepresent invention. Exemplary embodiments may be in accordance with anyone or more of the ones as listed below.

Embodiment 1

An electrochromic device comprising:

-   -   a substrate;    -   a first transparent conductive oxide layer over the substrate;        and    -   a first bus bar over the substrate, wherein the first bus bar        includes silver and has:        -   a resistivity of at most 8.0×10⁻⁶ Ω*cm;        -   an adhesion strength to SiO₂ of at least 3N based on 20            measurements, as determined by Method A of ASTM B905-00            (Reapproved 2010);        -   an average adhesion strength to SiO₂ of at least 3 based on            20 measurements, as determined by Method B of ASTM B905-00            (Reapproved 2010); or        -   a combination thereof.

Embodiment 2

The electrochromic device of Embodiment 1, further comprising anoxidation-resistant layer (1) between the substrate and the firsttransparent conductive oxide layer or (2) over the first transparentconductive oxide layer.

Embodiment 3

A process of forming an electrochromic device comprising:

-   -   forming a first transparent conductive oxide layer over a        substrate;    -   forming a bus bar precursor over the substrate, wherein the bus        bar precursor includes silver; and    -   firing the bus bar precursor to form a first bus bar, wherein        firing is performed such that the first bus bar is at a        temperature of at least 390° C.

Embodiment 4

The process of Embodiment 3, further comprising forming anoxidation-resistant layer, such that the oxidation-resistant layer is(1) between the substrate and the first transparent conductive oxidelayer or (2) over the first transparent conductive oxide layer.

Embodiment 5

The process of Embodiment 3 or 4, wherein forming theoxidation-resistant layer is performed by a sputter depositiontechnique.

Embodiment 6

The process of any one of Embodiments 3 to 5, wherein firing the bus barprecursor is performed such that the first bus bar is at a temperatureof greater than 400° C., at least 425° C., at least 450° C., or at least475° C.

Embodiment 7

The process of any one of Embodiments 3 to 6, further comprisingremoving organic material from the bus bar precursor after forming thebus bar precursor over the substrate and before firing the bus barprecursor.

Embodiment 8

The process of Embodiment 7, wherein removing the organic material isperformed at a temperature of at most 350° C., at most 325° C., or atmost 300° C.

Embodiment 9

The process of any one of Embodiments 2 to 8, wherein firing the bus barprecursor is performed after forming the first transparent conductiveoxide layer.

Embodiment 10

The process of any one of Embodiments 2 to 9, further comprising shapingthe electrochromic device after firing the bus bar precursor, whereinbending is performed at a temperature of at least 600° C.

Embodiment 11

The electrochromic device or the process of any one of Embodiments 2 and4 to 9, wherein the oxidation-resistant layer comprises silicon nitride,aluminum nitride, titanium nitride, tungsten nitride, tantalum nitride,titanium silicon nitride, tungsten silicon nitride, or tantalum siliconnitride.

Embodiment 12

The electrochromic device or the process of any one of the precedingEmbodiments, wherein the first bus bar has a resistivity of at most6.0×10⁻⁶ Ω*cm, at most 5.0×10⁻⁶ Ω*cm, at most 4.0×10⁻⁶ Ω*cm, or at most3.0×10⁻⁶ Ω*cm.

Embodiment 13

The electrochromic device or the process of any one of the precedingEmbodiments, wherein the first bus bar has a resistivity greater than1.59×10⁻⁸ Ω*cm.

Embodiment 14

The electrochromic device or the process of any one of the precedingEmbodiments, wherein the first bus bar has an average adhesion strengthto SiO₂ of at least 3 N, at least 5 N or at least 7N based on 20measurements as determined by Method A of ASTM B905-00 (Reapproved2010).

Embodiment 15

The electrochromic device or the process of any one of the precedingEmbodiments, wherein the first bus bar has a classification of at least3 or at least 4 as determined by Method B of ASTM B905-00 (Reapproved2010).

Embodiment 16

The electrochromic device or the process of any one of the precedingEmbodiments, wherein the first bus bar has an average adhesion strengthto SiO₂ of at most 1000 N based on 20 measurements, as determined byMethod A of ASTM B905-00 (Reapproved 2010).

Embodiment 17

The electrochromic device or the process of any one of the precedingEmbodiments, wherein the first transparent conductive oxide layercomprises a doped metal oxide.

Embodiment 18

The electrochromic device or the process of any one of the precedingEmbodiments, wherein the doped metal oxide comprises a tin oxide dopedwith a Group 13 element, a zinc oxide doped with a Group 13 element, orany combination thereof.

Embodiment 19

The electrochromic device or the process of any one of the precedingEmbodiments, further comprising:

-   -   a first electrode that is an electrochromic electrode or a        counter electrode;    -   a second electrode that is the other of the electrochromic        electrode or a counter electrode;    -   a ceramic electrolyte layer disposed between the first electrode        and the second electrode; and    -   a second transparent conductive oxide layer that is closer to        the second electrode than to the first electrode,    -   wherein the first transparent conductive oxide layer is closer        to the first electrode than to the second electrode.

Embodiment 20

The electrochromic device or the process of Embodiment 19, furthercomprising a second bus bar including silver, wherein the first bus baris electrically connected to the first transparent conductive oxidelayer, and the second bus bar is electrically connected to the secondtransparent conductive oxide layer.

Embodiment 21

The electrochromic device or the process of any one of the precedingEmbodiments, further comprising an insulating layer overlying theoxidation-resistant layer, wherein the insulating layer comprises anoxide.

Embodiment 22

The electrochromic device or the process of Embodiment 21, furtherwherein the insulating layer comprises SiO₂.

Embodiment 23

The electrochromic device or the process of any one of the precedingEmbodiments, wherein the substrate includes at most 1 wt. % of an alkalimetal oxide.

Embodiment 24

The electrochromic device or the process of Embodiment 22, wherein thesubstrate comprises a mineral glass layer.

Embodiment 25

The electrochromic device or the process of Embodiment 24, wherein themineral glass layer has a thickness of at most 300 microns.

Embodiment 26

The electrochromic device or the process of any one of the precedingEmbodiments, wherein the substrate is flexible.

Note that not all of the activities described above in the generaldescription or the examples are required, that a portion of a specificactivity may not be required, and that one or more further activitiesmay be performed in addition to those described. Still further, theorder in which activities are listed is not necessarily the order inwhich they are performed.

Certain features that are, for clarity, described herein in the contextof separate embodiments, may also be provided in combination in a singleembodiment. Conversely, various features that are, for brevity,described in the context of a single embodiment, may also be providedseparately or in any subcombination. Further, reference to values statedin ranges includes each and every value within that range.

Benefits, other advantages, and solutions to problems have beendescribed above with regard to specific embodiments. However, thebenefits, advantages, solutions to problems, and any feature(s) that maycause any benefit, advantage, or solution to occur or become morepronounced are not to be construed as a critical, required, or essentialfeature of any or all the claims.

The specification and illustrations of the embodiments described hereinare intended to provide a general understanding of the structure of thevarious embodiments. The specification and illustrations are notintended to serve as an exhaustive and comprehensive description of allof the elements and features of apparatus and systems that use thestructures or methods described herein. Separate embodiments may also beprovided in combination in a single embodiment, and conversely, variousfeatures that are, for brevity, described in the context of a singleembodiment, may also be provided separately or in any subcombination.Further, reference to values stated in ranges includes each and everyvalue within that range. Many other embodiments may be apparent toskilled artisans only after reading this specification. Otherembodiments may be used and derived from the disclosure, such that astructural substitution, logical substitution, or another change may bemade without departing from the scope of the disclosure. Accordingly,the disclosure is to be regarded as illustrative rather thanrestrictive.

What is claimed is:
 1. An electrochromic device comprising: a substrate;and a first bus bar over the substrate, wherein the first bus barincludes silver and has: a resistivity of at most 8.0×10⁻⁶ Ω*cm.
 2. Theelectrochromic device of claim 1, further comprising a first transparentconductive layer over the substrate, an oxidation-resistant layer (1)between the substrate and the first transparent conductive oxide layeror (2) over the first transparent conductive oxide layer.
 3. Theelectrochromic device of claim 2, wherein the oxidation-resistant layercomprises silicon nitride, aluminum nitride, titanium nitride, tungstennitride, tantalum nitride, titanium silicon nitride, tungsten siliconnitride, or tantalum silicon nitride.
 4. The electrochromic device ofclaim 2, wherein the first transparent conductive oxide layer comprisesa doped metal oxide.
 5. The electrochromic device of claim 4, whereinthe doped metal oxide comprises a tin oxide doped with a Group 13element, a zinc oxide doped with a Group 13 element, or any combinationthereof.
 6. The electrochromic device of claim 1, wherein the first busbar has a resistivity of at most 6.0×10-6 Ω*cm.
 7. The electrochromicdevice of claim 1, wherein the first bus bar has a resistivity of atmost 5.0×10-6 Ω*cm.
 8. The electrochromic device of claim 1, wherein thefirst bus bar has a resistivity of at most 4.0×10-6 Ω*cm.
 9. Theelectrochromic device of claim 1, further comprising: a first electrodethat is an electrochromic electrode or a counter electrode; a secondelectrode that is the other of the electrochromic electrode or a counterelectrode; a ceramic electrolyte layer disposed between the firstelectrode and the second electrode; and a second transparent conductiveoxide layer that is closer to the second electrode than to the firstelectrode, wherein the first transparent conductive oxide layer iscloser to the first electrode than to the second electrode.
 10. Theelectrochromic device of claim 2, further comprising an insulating layeroverlying the oxidation-resistant layer, wherein the insulating layercomprises an oxide.
 11. The electrochromic device of claim 10, furtherwherein the insulating layer comprises SiO₂.
 12. An electrochromicdevice comprising: a substrate; and a first bus bar over the substrate,wherein the first bus bar includes silver and has: an average adhesionstrength to SiO₂ of at least 3N based on 20 measurements, as determinedby Method A of ASTM B905-00 (Reapproved 2010).
 13. The electrochromicdevice of claim 12, wherein the first bus bar has an average adhesionstrength to SiO₂ of at least 5 N based on 20 measurements as determinedby Method A of ASTM B905-00 (Reapproved 2010).
 14. The electrochromicdevice of claim 12, wherein the first bus bar has an average adhesionstrength to SiO₂ of at least 7 N based on 20 measurements as determinedby Method A of ASTM B905-00 (Reapproved 2010).
 15. The electrochromicdevice of claim 12, further comprising a first transparent conductivelayer over the substrate, an oxidation-resistant layer (1) between thesubstrate and the first transparent conductive oxide layer or (2) overthe first transparent conductive oxide layer.
 16. An electrochromicdevice comprising: a substrate; and a first bus bar over the substrate,wherein the first bus bar includes silver and has an average adhesionstrength to SiO₂ of at least 3 based on 20 measurements, as determinedby Method B of ASTM B905-00 (Reapproved 2010).
 17. The electrochromicdevice of claim 16, wherein the first bus bar has a classification of atleast 4 as determined by Method B of ASTM B905-00 (Reapproved 2010). 18.The electrochromic device of claim 16, further comprising a firsttransparent conductive layer over the substrate, an oxidation-resistantlayer (1) between the substrate and the first transparent conductiveoxide layer or (2) over the first transparent conductive oxide layer.19. The electrochromic device of claim 16, wherein theoxidation-resistant layer comprises silicon nitride, aluminum nitride,titanium nitride, tungsten nitride, tantalum nitride, titanium siliconnitride, tungsten silicon nitride, or tantalum silicon nitride.
 20. Theelectrochromic device of claim 16, wherein the first transparentconductive oxide layer comprises a doped metal oxide.